Anthraquinone dyes



ANTHRAQUINONE DYES Roy A. Pizzarello, Mount Vernon, and Boris Gutolf, Far I Rockaway, N. Y., assignors to Intel-chemical Corporation, New York, N.'Y., a corporation of Ohio No Drawing. Application January 26, 1954, Serial No. 406,332

6 Claims. (Cl. 260-380) The present invention relates to new dyes; more particularly the invention relates to dyes which are derivatives of anthraquinone and which dye cellulose acetate and synthetic textiles, such as Dacron, in bright red shades.

Our new dyes can be represented as having the following structural formula:

O NH;

1! l R H 0 O OH where R is hydroxyl, an alkoxy group containing one to four carbon atoms, an hydroxyalkyl group containing one to four carbon atoms, or an hydroxyalkoxy group con- Y taining two to four carbonatoms. These new'd'yes are conveniently prepared by condensing 1-amino-2-halo-4- hydroxy anthraquinone with alkali metal salt of a substituted phenol having the formula:

where R has the significance previously assigned to it. Typical examples of such phenols include hydroquinone, resorcinol, hydroquinone monomethyl ether, resorcinol monoethyl ether, m-hydroxy benzyl alcohol, .fi-(p-hydroxyphenyl) ethyl alcohol, m-(B-hydroxyethoxy) phenol, p-(p-hydroxyethoxy) phenol, and monoglycerol ether of resorcinol."

- Cellulose acetate dyes are known which are derived from l-amino-2-halo-4-hydroxy anthraquinone or 1,4- 111-.

diamino-Z-halo-anthraquinone.by replacing the halogen atom with an alkoxy group. These dyes generally have poor gas fading properties and do not have very good affinity for cellulose acetate. Also, these known-dyes,

especially those derived from l-amino-Z-haloA-hydroxy 11;-

anthraquinone, tend to sublime, i. e; their color is trans ferable to white backgrounds or to other fabrics of a different color, when the dyed fabric is heated as in laundering and ironing. The new dyes of the present invention overcome these bad characteristics of these a for minutes.

m t 2,773,071 Patented Dec. 1956 taining 0.42 grams of impure dyestufr'. The dyestuff was purified by passing a benzene solution of the "crude material over a column of magnesium carbonate. Analysis of the purified dye showed a nitrogen content of 3.73% While the nitrogen content calculated for l-amino-Z-(mhydroxymethyl phenoxy) 4-hydroxy anthraquinone is 3.88%. This dye hasthe following formula:

The dye, when dispersed in conventional manner, had good afiinity for, and dyed cellulose acetate fibers a bright red shade of good resistance to light and gas fading. The dye does not sublime.

Example 1 -amino 2 bromo 4-hydroxy anthraquinone (32.16 grams), hydroquinone (96.14 grams) and potassium carbonate (13.8 grams) were heated to 180 C. and kept at that temperature for two hours. Water (200 grams) was added to the'cooled reaction mass, then the mixture was heated up to nearthe boil, filtered hot, and the impure solid dyestuff dried. The yield of dye was 38.77 grams. It dyed cellulose acetate a bright,'non-subliming red shade of good resistance to light and gas fading. It dyed Dacron fibers .(polyester fiber made from terephthalic acid andglycol) fibers a bright, bluish red shade of good fastness properties and was non-subliming. This dye has the probable formula: s

O. NH:

Example 3 Resorcinol (180 grams), 1-amino-2-bromor4-hydroxy anthraquinone (31.9 grams), and potassium carbonate (16 grams) were heated to 175 C. and kept at 175 to 180 for minutes. The reaction mixture was then dropped into two liters of water, boiled, :and filtered.

The impure dyestufi was purified by dissblvin'g it in hot Example 4 m-(fl-Hydroxyethoxy phenol- (5 grams), potassium carbonate (0.4 g r2 1r r 1 )-"and 1-amino-2-bromo-4-hydroxy A anthraquinone (0.96 gram) were fheated at -180 C.

Then 40 ml. o'f*25%-. aqueous caustic soda solution was added and the mixture was drowned in 300 ml. of water, filtered and dried. The crude dye was purified in aimanner similar to that ofExample 1.

The dye has good afiinity'for, and dyes cellulose acetate and Dacron fibers a verybright and fast red shade andis substantially non-subli'rning. This dye has the probable formula:

NH: O-CHzCHzOH Example In a manner similar to Example 4, p- (fl-hydroxyethoxy)-phenol was reacted with 1-amino-2-bromo-4- hydroxy anthraquinone to obtain a red dye having the probable formula:

0 ill I oQo-omomon 0 v v i) on This dye has good afiinity for, and dyes cellulose acetate and Dacron fibers red shades that are non-subliming, and have good fastness properties.

Example 6 In a manner similar to Example 4, the monomethyl ether of hydroqui none was reacted with l-amino-Z- bromo-4-hydroxy anthraquinone to obtain a dye having the probable formula:

ii OH This dye has good aflinity. for, and dyes cellulose acetate and Dacron bright red shades that are fast to light and gas fading and are substantially non-subliming.

Example 7 In a manner similar Example 4, the monoglycerol ether of resorcinol was reacted with 1-an1ino-2-bromo-4- hydroxy anthraquinone to give a dye having the probable This dye has good aflinity for cellulose acetate and Dacron fibers and dyes a bright shade of red having good fastness properties and is substantially non-subliming.

Example 8 In a manner similar to Example 4, catechol was condensed with l-amino-2-bromo-4-hydroxy anthraquinone to give a dye having the probable formula:

This dye has good aflinity for cellulose acetate and dyes a bright shade of red having good gas and light fastness' and is substantially non-sublimiug.

Example 9 In a manner similar to Example 4, the monomethyl ether of resorcinol was condensed with l-amino-Z-bromo- 4-hydroxy anthraquinone to give a dye having the probable formula:

This dye has good alfinity for cellulose acetate and dyes a bright shade of red having good gas and light fasteness. It has better washfastness than the dye obtained in Example 3 and is substantially non-subliming.

v Example 10 In a manner similar to Example 4, o-(fl-hydroxyethoxy) phenol was condensed with 1-amino-2-bromo- 4-hydroxy anthraquinone to give a dye having the probable formula:

(II!) IITH: ?OH2CH:OH in; i) 011 We claim: A new fed y i g e Structural formula:

two to four carbon atoms.

2. A new red dye having the formula:

ii I O OH I 3. A new red dye having the formula:

4. A new red dye having the formula:

a) NH;

: O-Ooanmomon OH I V 5 5. A new red dye having the formula:

0 NH: CHBOH 6. A new red dye having the formula:

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Georgievics-Dye Chemistry, pages 6, 7 (1920). 

1. A NEW RED DYE HAVING THE STRUCTURAL FORMULA: 